Treatment of materials made of or containing cellulose derivatives



Patented Aug. 30, 1932 UNITED STATES GEORGE HOLLAND ELLIS, or sronnon,

PATENT OFFICE NEAR DERBY, ENGLAND, ASSIGNOR 'ro CELANESE conronarron or AMERICA, A conromrronor DELAWARE I TREATMENT OF MATERIALS MADE OF OR CONTAINING CELLULOSE DERI V ATIVES No Drawing. Application filed October 12, 1928, Serial No. 312,221, and in Great Britain November 2, 1927.

This invention relates to the treatment of yarns, threads, knitted or woven fabrics or other materials made of orcontaining cellulose acetate or other organic acid esters of cellulose for example cellulose formate, propionate or butyrate or the productsobtained by the treatment of alkalied cellulose with sulpho-chlorides, e. g. the product known as immunized cotton obtained from cotton and p-toluene sulpho-chloride, or made of or containing cellulose ethers, such for instance as methyl, ethyl or benzyl cellulose or the corresponding condensation products of cellulose and glycols or other polyhydric alcohols, all of which cellulose derivatives are hereinafter referred to as organic substitution derivatives of cellulose.

According to the present invention materials made of or containing cellulose acetate or other organic substitution derivatives of cellulose are treated with alkaline solutions of tin. Solutions of sodium or potassium stannates are .very suitable for use in the processes of'the present invention.

The materials treatedaccording to the present-invention undergo an increase in weight due to the absorption of stannic oxide most probably in a hydrated form, the absorption of the metallic radicle in' the case of materials made of or containing cellulose esters being more than suflicient to counterbalance any loss in weight due to partial saof the\cellulose ester. The materiahgpar icularly when treated in yarn or fabric form, also acquire an increased re sistance to hot treatments such as ironing.

The greatest advantage accruing from the present invention, more especially with ma terials made of or containing cellulose esters,

is that the materials treated exhibit an affinity for a very wide variety of coloring matters. Thus not only do cellulose ester materials so treated retain their afiinity for: basic colors and for the insoluble colors especially devised for application thereto and usually appliedas such in solubilized or dispersed form, e. g. the S. R. A. colors, but they also exhibit an aflinity for the direct cotton colors, for mordant colors both synthetic and tions of the alkaline solutions. The process may be conducted continuously b mechanical impregnation, the material eing then allowed time to absorb the necessary quantity of alkaline solution or it may be carried out by a simple immerslon in thebath or by any other suitable method. The immersion meth- 0d appears to give the best results.

Absorption of the alkaline solutions may be assisted by addition of swelling agents for the cellulose derivatives, for example thiocyanates, particularly of the alkali metals or-ammonlum.

It is-further found that the treatment of the materials with alkaline solutions of tin enables the production thereon of discharge eifects, which hitherto have been very difficult of attainment on these materials. The invention accordingly further comprises the production of discharge effects on materials made of orcontaining cellulose acetate or other organic substitution derivatives of cellulose treated with alkaline solutions of tin, for example alkali stannates, either by dyeing, printing or otherwise coloring with dischargeable dyestuffs and subsequently applying ischarges as required or by applying discharges at selected places and subsequent- 1y; dyeingor otherwise coloring with the-disc argeable dyestuifs. Colored discha-r es may be employed containing undischargea le be the orothers 6 15.9% Na) and 250 more soluble body and thereby facilitating washing out.

T e simple reduction discharges may be applied, for example, for discharging direct cotton dyestuffs or insoluble dischargeable azo dyestufl's which have been applied in dispersed form. Together with the leucotropic bodies referred to above they maybe In addition to being applicable to mate-' rials made entirely of cellulose esters and the processes of the present invention may alsobe applied to mixed goods containing, such cellulose derivatives in association with other fibres or materials not deleteriously or substantially afi'ected by'the alkaline solutions employed, for example with cotton or with artificial cellulosic fibres, such for instance as viscose and cuprammonium artificial silks. Furthermore effects may be obtained by weaving, knitting or otherwise making up yarns or threads, containing organic substitution derivatives of cellulose which have been treated .with alkaline solutions of tin, with other yarns or threads, for 7 example wool or silk which may be deleteriously affected by the alkaline solutions, and thereafter dyeing with or without dischargin The following examples are illustrative of the processes of the invention, but are not to be regarded as limiting it Example 1 A solution is prepared. containing 150 grams per litre'of commercial sodium stannate (containing for example 41.6% Sn and ams per litre of sodium thiocyanate. Cell ose acetate fabric is immersed in the bath (weight 30 :1 on the goods) at 25 C. for. one hour and is then lifted, drained and washed off well. The fabric is given a soap treatment with 2.5 grams per litre of soap for 20 minutes at 40 C. and finally washed off. thoroughly in cold or warm water. The fabric is dried or otherwise treated as required. It shows a considerable loading (by ash about 8.5%).

Thefa'bric so treated may be dyed by means of '(dgsestulfs of various types by standard meth Direct cotton dyeemfis g. the sodium salt of p-sulpho benzene azo benzene azo-6- estufi's which are applied 1234) dyes the treated fabric a full (1) Caledon' Jade Green, dimethoxy-- dibenzanthrone (Colour Index No. 1101) dyes the treated fabric a full green shade from a hydrosulphite vat, while'under the same conditions the untreated fabric shows no useful aflinity.

(2) Indanthrene Red Violet R. R. K, 3C4- dichlor-1.2-anthraquinone-acridone (Colour Index No. 1161) dyes the treated fabric the full red violet from a hydrosulphite vat.

(3) Algol Scarlet G, l-benzoylaminolmethoxy-anthraquinone Colour Index No. 1129) dyes the treated fa ric scarlet from a hydrosulphite vat.

l'ndz'goz'd 'vat dyestuffs g. Indigo L. L. pdr. (Colour Index No. 1177) dyes the treated fabric blue from a hydrosulphite vat.

Mordant dyestufi's:e. g. Alizarin (Colour Index'No. 1027) gives the true orange lake on e the treated fabric from aqueous solution.

Natural dyestu;fs:

(1) Hematine (Colour Index No. 1246) 'ves a full black shade on .the treated fabric rom aqueous solution.

(2) Persian berries (Colour Index No.

yellow from aqueous solution. 7

Basic dyestu fs g. Rhodamine B,

h drochloride of diethyl-m-amino phenolplithalein (Colour Index No. 749) dyes the treated fabric a full bluish pink'from a bath acidified with acetic acid.

Insoluble colours for cellulose acetate:-,

e. g. p-nitrobenzene a zo di henylamine dyesa full orange by any of the Ewample 2 A solution of 300 grams per litre of sodium stannate (containin for example 35.80% Sn and 21.03% Na) 15 prepared and a celluown methods.

lose acetate woven fabric mechanically impregnated therewith at 25 C. so as to contain approximately its own weight of liquor. The I fabric is rolled up and left for 3 hours. Itis then washed off thoroughly in water, treated for )6 hour in a 10%disodium hydrogen phosphate solution at 4045 C., washed off thoroug'hly, soaped for 20 minutes in a 2.5 gram, per litre soap solution at 40 C., washed off again and dried or otherwise treated as required. The fabric so treated may be dyed in a similar manner to that indicated ample 1. I

'yarn, after treating with alkaline stannate according to the above examples is .dyed with 1% of its weight, of Chlorazol Violet "R;

(Colour Index 388). The material is then inEx-- dried and further-prepared for printing as desired. It is then printed by roller printing machine or hand-block with a printing pas composed as follows 540 grams gum arabic 1:1. 180 grams Caledon Jade Green paste a (Colour Index 1101). 36 grams sodium hydrosulphite. 36 grams caustic soda. 120 grams anthraquinone 10% paste. 108 grams methylated spirit. Heat to reduce, cool partly and add 180 grams formosul (sodium formaldehyde sulfo'xylate).

After printing, the material is dried and steamed in the cottage steamer for 3 to 4 minutes with steam at 5 lbs. pressure, or alternatively given a passage through the rapid ager at 100 C. after which it is' given a treatment for 5 minutes at 60 C. in an oxidizing bath, composed of 1 gram per litre sodium perborate. 1 gram per litre soap. After oxidation the fabric is washed, soaped and otherwise treated and finished'as desired or requisite.

v Ewample 4 A fabric composed of cellulose acetate yarns, which has been treated with alkaline stannate according to the Examples 1 or 2 above is dyed with 0.5% of its weight of 4- nitro-Q-methoxybenzene-azo-diethyl aniline, after which the material is dried and further finished-for printing as desired. It is then printed on a roller printing machine or by hand-block with the following printing paste: Y

720 grams gum arabicl 1. 120 grams anthraquinone 10% paste.

60 grams oxide. 100 grams water. 200 grams formosul (sodium formaldehyde sulfoxylate). v

After printin the fabric is dried and steamed in the cottage steamer for 5 to 7 minuteswith steam at 5 lbs. pressure or given one or two passages through the rapid a er' at 100 C. The material is then was ed, soaped and otherwise treated and finished as desired or requisite. 7

Example 5 A fabric composed of cellulose acetate yarn, after treatment with alkaline stannate according to Examples 1 or 2, above, is printedon a roller printing machine or by handblock with apaste consisting of 180 grams Lucotrope O (dimethylphenylbenzylammonium chloride). 1020 grams British gum thickening.

After printing the material is dried and agam printed, using a cover roller, with an anthraquinone vat color paste as follows 624 grams gum arabic 1: 1. 240 grams Caledon Red BN. paste (Colour Index 1162).. 36 grams caustic soda. 60 grams Turkey red oil. 60 grams methylated spirit. 36 grams sodium hydrosulphite.

Heat up to reduce, cool and add 144 grams formosul-lzl.

After printing the material is given a passage through the rapid ager at 100 C. or alternatively given an equivalent steaming of about 4 minutes in the cottage steamer at 5 lbs. pressure, after which it is oxidized in a 5 gram litre solution of sodium dichromate for 5 minutes at 60 C. Itis then washed, soaped and otherwise treated and finished as desired or requisite.

In a similar manner materials containing other cellulose esters, for example cellulose formate or cellulose propionate, or immunized cotton, or materials containing cellulose ethers, for instance methyl, ethyl or benzyl cellulose, may be treated to obtain similar effects.

What I claim and desire to secure by Letters Patent is 1. Process for the treatment of materials comprising cellulose esters, comprising treating the materials with solutions of alkali metal stannates. v i

2. Process for the treatment of materials comprising cellulose esters, comprising treatboth discharges and dischargeable dyestufl's.

Process for the treatment of materials comprising cellulose acetate, comprising treating the materials with solutions of al- -kali metal stannates.

6. Process-for the treatment of materials comprising cellulose acetate, comprising treating the materials with solutions of al-' kali metal stannates and thereafter coloringthe materials.

7. Process for the treatment of materials comprising cellulose acetate, 7 comprising treating the materials with solutions of alkali metal stannates and thereafter coloring the materials with dyestuffs normally applied to cotton. p

8. Process for the treatment of materials comprising cellulose acetate, comprising treating the materials with solutions of alkali metal stannates and thereafter locally coloring the materials by applying separately both discharges and dischargeable dye stuffs.

9. Process for the treatment of materials comprising cellulose acetate, comprising treating the materials with solutions of a1- kali metal stannates and thereafter locally coloring the materials by applying separately both discharges and dischargeable dyestufl's normally applied to cotton.

10. Process for the treatment of materials comprising cellulose acetate, .comprising treating the materials with solutions of alkali metal stannates and thereafter locally coloring the materials by uniformly coloring with dischargeable dyestuffs and thereafter locally applying discharges. j

11. Process for the treatment of materials comprising cellulose acetate, comprising treating the materials with solutions of alkali metal stannates and thereafter locally coloring the materials by uniformly coloring with dischargeable dyestuffs and thereafter locally applying colored discharges.

\ 12. Process for the treatment of materials comprising cellulose acetate, comprising treating the materials with solutions of al- ,kali metal stannates and thereafter locally coloring the materials by uniformlyroloring with dischargeable dyestuffs and thereafter locally applying reduction discharges.

13. Process for the treatment of materials. comprising cellulose acetate, comprising treating the materials with solutions of alkali metal stannates and thereafter locally coloring the materials by uniformly coloring with dischargeable dyestuffs and thereafter locally applying colored reduction dis charges.

4 In testimony whereof I have hereunto subscribed my name. i r

60 GEORGE HOLLAND ELLIS. 

